JPH1121378A - Antimicrobial or antifungal resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. that gives a molded article, which is excellent in antimicrobial capability and from which an antimicrobial component easily bleeds to the surface, by compounding a resin component with a metal-based antimicrobial or antifungal component and a hydrophilic component. SOLUTION: This compsn. contains 100 pts.wt. resin component (e.g. an acrylonitrile-styrene copolymer), 0.1-30 pts.wt., pref. 0.3-5 pts.wt., metal-based antimicrobial or antifungal component pref. formed by causing potassium titanate, zeolite, or zirconium phosphate to carry silver and/or zinc, and 0.1-30 pts.wt., pref. 2-6 pts.wt., hydrophilic component pref. having a hydrophlicity expressed by water absorption according to ASTM D-570 of 3.5% or higher (e.g. a polyethylene oxide-polyether-polyamide block copolymer). If necessary, the compsn. further contains an org. antimicrobial or antifungal component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial or antifungal resin composition applied to, for example, films, plastics, fibers and the like, and uses thereof.

[0002]

2. Description of the Related Art Conventionally, products using plastics containing an antibacterial agent or an antifungal agent in, for example, refrigerators, washing machines, dish dryers, telephones and the like are known. Specifically, it is used for a lid of a vegetable room of a refrigerator, a wall material in a refrigerator, a food tray, a washing tub of a washing machine, a drainage basket of a dish dryer, a telephone receiver, and the like. In these products, plastics containing an antibacterial agent or an antifungal agent (hereinafter may be simply referred to as an antibacterial agent) include polypropylene, ABS resin, A
Many S resins, polyethylene, polystyrene,
Examples include polyvinyl chloride (PVC).

[0003]

Although plastic products containing these antibacterial agents are expected to have antibacterial properties, when molded into products, a skin layer of resin alone is formed near the surface, and this skin layer is formed. However, there is a problem that sufficient antibacterial properties cannot be obtained because bleeding out of the antibacterial agent to the surface is prevented. Such a problem is particularly remarkable in a metal antibacterial agent, and when an organic antibacterial agent is used, although some antibacterial properties can be exhibited depending on a resin, depending on a resin type such as an AS resin or an ABS resin. Some of them did not exhibit antibacterial properties. On the other hand, fibrous metallic antibacterial agents, such as those carrying silver on potassium titanate fiber, are preferably used because they impart antibacterial performance and have a reinforcing effect, but these fibrous inorganic substances are used as molded products. In this case, there is a drawback that the above-mentioned problem is promoted in order to facilitate the formation of a skin layer on the surface of the molded article by orientation. An object of the present invention is to provide a resin composition having more excellent antibacterial performance and a use of a molded article obtained therefrom.

[0004]

The present invention provides an antibacterial or antifungal composition comprising a resin component (A), a metal antibacterial or antifungal component (B), and a hydrophilic component (C). The present invention relates to a resin composition and its use. In the present invention, antibacterial performance can be improved by intentionally forming paths for water molecules and the like in the resin constituting the molded article, so that the antibacterial component is easily eluted on the product surface.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the resin component (A) of the present invention, various resins such as thermoplastic and thermosetting or reaction-curing resins can be used, whether natural resins or synthetic resins. Good. Specific examples of the thermoplastic resin include polyethylene, polypropylene, 5-methylpentene resin, polyvinyl chloride (PVC), polyvinylidene chloride,
Polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyamide, polystyrene, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), fluororesin,
Thermoplastic polyester, polycarbonate, polyacetal, polyphenylene sulfide, polyarylate (PAR), polyphenylene ether, polysulfone, polyethersulfone (PES), polyethernitrile, polyetherimide (PEI), polyetheretherketone (PEEK), etc. Can be mentioned.

Specific examples of the thermosetting or reaction curable resin include phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, vinyl ester resin, alkyd resin, silicone resin, diallyl phthalate resin, bis Examples thereof include a maleimide triazine resin, a polyimide, a urea resin, and a polyurethane resin. Further, vinylidene fluoride-hexafluoropropylene (VDF-HFP) elastomer, vinylidene fluoride-chlorotrifluoroethylene (VDF-
CTFE) Fluorine elastomers such as elastomers, polyolefin elastomers such as isobutylene rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene copolymer (SBS) And various elastomers such as styrene-based elastomers such as styrene-ethylene-butylene-styrene copolymer (SEBS), isoprene rubber, urethane rubber, epichlorohydrin rubber and silicone rubber.

In the present invention, the metal antibacterial or antifungal component (B) includes, for example, silicates such as zeolite, calcium silicate and magnesium metasilicate; silica gel;
Glass; phosphates such as calcium phosphate and zirconium phosphate; titanium oxide; zinc oxide; titanates such as potassium titanate; ceramics; Here, the metal may be a metal or a metal ion, and examples thereof include silver, zinc, copper, nickel, magnesium, and platinum. The shape of the component (B) is not particularly limited, and a powder, fibrous or other shape may be used. Specifically, for example, Baicam AK (Otsuka Chemical), Zeomic (Sinane Zeomic), Novalon (Toagosei), Bakutekira (Kanebo), Sylwell (Fuji Silysia), etc. can be mentioned. In the present invention, the expression "antibacterial or antifungal component" means a component having one or both of antibacterial and antifungal properties, and generally, it usually has one rather than both. , Depending on the intended use.

In the present invention, examples of the hydrophilic component (C) include a hydrophilic organic substance such as a water-soluble resin and a hydrophilic inorganic substance, and these may be water-absorbing or moisture-absorbing. For example, solubility in water (2
0 ° C.), more than 10 ⁻³ g / l, preferably 10 ⁻² g / l
Above, the water absorption is 2% or more according to ASTM D-570, preferably 3.5% or more, or the water absorption when immersed in water is 23 ° C and 10% by weight or more for 24 hours, preferably Is preferably 50% or more.

Specific examples of the hydrophilic resin include, for example, natural products such as agar, carrageenan, corn starch, guar gum, arabic gum, karaya gum, tragan gum, locust bean gum, potato, wheat, rice starch, tapioca starch and the like. it can. Chemically modified natural products include cationic starch, dextran, hydroxyalkyl starch, methylcellulose,
Examples thereof include sodium carboxymethylcellulose, xanthan gum, casein, gelatin, and glue. Synthetic products include polyamide (particularly polyamide 6), polyvinyl alcohol, ethylene vinyl alcohol copolymer,
Polyacrylamide, cationic resin, polyacrylic acid and its derivatives, polyethylene oxide, polyethylene oxide-methyl methacrylate copolymer, polyethylene oxide-polyamide copolymer, polyethylene oxide-polyesteramide copolymer, polyethylene oxide-epichlorohydrin Copolymer, polyethylene oxide-polypropylene oxide copolymer, poly-
Examples thereof include N-vinyl-2-pyrrolidone, a polyether-polyester-polyamide copolymer, a vinyl ether-based polymer, a styrene-maleic anhydride copolymer, and an ethylene-maleic anhydride copolymer. Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like used as antistatic agents can also be used in this application. Also, a so-called hydrophilic gel in which a hydrophilic polymer is slightly crosslinked can be preferably used. Specific examples of the hydrophilic gel include anionic cellulose derivatives, starch-polyacrylamide, polyvinylpyrrolidone, maleic acid polymers, acrylic acid polymers, and the like.

Specific examples of the hydrophilic inorganic substance include carbonate compounds such as magnesium carbonate, hydroxides such as zinc hydroxide, oxides such as magnesium oxide and zinc oxide, and the like.
Sulfate compounds such as barium sulfate and alum are exemplified. In the present invention, the above (A), (B), (C)
Component (B) is used in an amount of 0.1 to 30 parts by weight, preferably 0.3 part by weight, per 100 parts by weight of component (A).
The amount of component (C) is 0.1 to 30 parts by weight, preferably 2 to 6 parts by weight.

In the present invention, an organic antibacterial or antifungal component (B-1) can be used in combination with the metal antibacterial or antifungal component (B). This (B-1)
As the component, for example, ethyl alcohol, 2-bromo-
Alcohols such as 2-nitro-1,3-propanediol and N- (2-hydroxypropyl) -aminomethanol; phenols such as phenol, orthophenylphenol and 4-chloro-3,5-dimethylphenol; formaldehyde; Aldehydes such as glutaraldehyde, carboxylic acids such as benzoic acid, sodium benzoate, octanoic acid and calcium propionate; esters such as glycerin fatty acid ester and ethyl parahydroxybenzoate; 2,4,4'-trichloro Ethers such as -2'-hydroxydiphenyl ether, 2,4,5,6-
Tetrachloroisophthalonitrile, 1,2-dibromo-
Nitriles such as 2,4-dicyanobutane, hydrogen peroxide,
Peroxide-epoxy type such as ethylene oxide, halogen type such as parachlorophenyl-3-iodopropargyl formal, α-chloronaphthalene, 8-oxyquinoline,
Pyridine-quinoline, such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, N, N ', N "-
Triazines such as trishydroxyethylhexahydro-S-triazine, isothiazolones such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; 2- (4 -Thiocyanomethylthio) benzimidazole, imidazole-thiazoles such as 2- (4'-thiazolyl) -benzimidazole (TBZ), 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl-4,4 Anilides such as' -dichlorocarbanilide, biguanides such as polyhexamethylenebiguanidine hydrochloride, chlorhexidine gluconate, disulfides such as bis (dimethylthiocarbamoyl) disulfide, ammonium-N-methyldithiocarbamate, sodium Thioca such as -N-methyldithiocarbamate Bameto system, polyglucosamine, saccharide such as aminoglycosides, tropolone system such as hinokitiol, alkyl dimethyl benzyl ammonium chloride, octadecylamine acetate, alkyl (diaminoethyl) surfactant system such as glycine hydrochloride, 1
Organic antibacterial or antifungal components of organometallics such as 0,10'-oxybisphenoxalcin, zinc naphthenate, and copper naphthenate can be used. The proportion of the component (B-1) is 0.1 to 100 parts by weight of the component (A).
10 parts by weight, preferably 0.1 to 5 parts by weight.

In the present invention, when a fibrous material such as potassium titanate fiber carrying silver is used as a metal antibacterial or antifungal component, the metal antibacterial or antifungal agent is used as an antibacterial or antifungal improver. It is preferable to mix an inorganic substance having a shape different from that of the component, since the antibacterial or antifungal performance can be further improved. Examples of the improver include natural or artificial minerals and inorganic compounds. Specific examples include carbonate compounds such as calcium carbonate and magnesium carbonate, sulfate compounds such as barium sulfate and calcium sulfate, metal oxides such as alumina, clays such as kaolin and talc, and silica such as white carbon and mica. Examples include acid compounds, but are not limited thereto. That is, these improvers are used to control the orientation of the fibrous antibacterial / antifungal agent when the fibrous antibacterial / antifungal agent is oriented at the time of molding to form a skin layer containing no antibacterial agent on the surface of the molded article. Since the antibacterial property is improved by the action of suppressing by disturbing, the shape may be granular, plate-like, massive, irregular, rod-like, scale-like, etc. Good. The size of such an enhancer is usually 0.1 μm to 1 mm in average particle size.
Degree, preferably about 1 to 100 μm. When the fibrous antibacterial agent is a fine fibrous material having a diameter of about 0.1 to 3 μm, short glass fibers or carbon fibers having a diameter of 10 μm or more may be suitably used as the antibacterial and antifungal agent. it can. The compounding ratio of the antibacterial / antifungal agent is 10 to 3000 parts by weight, preferably 50 to 1000 parts by weight, per 100 parts by weight of the fibrous metal antibacterial agent to be compounded.

In the present invention, other compoundable ingredients include dyes and pigments for coloring, and glass fiber, carbon fiber, potassium titanate fiber, wollastonite, talc, mica, calcium carbonate for improving physical properties. Reinforcing agents and fillers such as titanium oxide, silica, aramid fiber, wood flour, etc., for imparting flame retardancy, phosphoric acid esters such as tris (dichloropropyl) phosphate and bromophosphonate, and halogens such as tetrabromoethylene Flame retardants such as fluorinated hydrocarbons, antimony oxide, zinc borate or phosphorus-containing polyols; light stabilizers such as salicylates, benzotriazoles and hindered amines to impart weather resistance; 2,6-di-tert-butyl-p-cresol (BH
T) 2,2'-thiobis (4-methyl-6-t-butylphenol), dilaurylthiodipropionate (TP
L), an antioxidant such as nonylphenyl phosphite and naphthylamine, a foaming agent such as azodicarbonamide for foaming, a compatibilizer when using a multi-component resin, and improving the dispersibility of each component. Various surfactants, such as anionic, cationic, and nonionic surfactants, can be used for the purpose of preventing or preventing static electricity or improving the hygroscopicity.

In the production of the present invention, a usual mixing operation, for example, a Banbury mixer method, an internal mixer method, an extrusion granulation method and the like can be appropriately employed. The mixing operation can be performed prior to or during molding. When a mixing operation is performed prior to molding, the obtained resin composition of the present invention can be distributed and stored as pellets using various pelletizers or the like. In addition, a masterbatch in which the component (A) blended in a smaller amount than the prescribed amount and the component (B) and (C) components blended in a larger amount than the prescribed amount and other components blended as necessary are mixed by these methods in advance. A method in which pellets composed of only the component (A) are mixed with the master batch at the time of molding and then supplied to a molding machine can also be preferably used.

The resin composition of the present invention can be used as a molded article having antibacterial or antifungal properties by molding and spinning into a desired shape. When the resin composition of the present invention is formed into a molded product, various molding methods such as injection molding, extrusion molding, blow molding, transfer molding, press molding, lamination molding, and calendar molding can be used. Examples of molded articles include air conditioner filters, blower fans, covers, etc., lids for refrigerator vegetable compartments, ice machine hoses, ice machine water trays, wall materials in the refrigerator, food trays, washing tubs for washing machines, dish dryers Drain basket, telephone handset,
The outside of the main body container of the rice cooker, the toilet seat of the toilet, the unit bath, the housing of the remote controller, the decorative board, the handle of the automobile, the belt conveyor, the toy, the stationery, the housing of the air purifier, the internal driving parts, and the like can be exemplified. Further, the resin composition of the present invention can be converted into fibers by further stretching after spinning or extrusion. The obtained fiber can be made into a textile product such as a cloth or a net by knitting or weaving. In addition, any method other than molding, spinning, extrusion, and stretching can be used, which can be used as a product using the resin composition of the present invention. For example, paint,
It can be used as glue, wallpaper, water treatment agent and the like.

[0016]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. Examples 1 to 5 and Comparative Examples 1 to 2 After dry blending each component (parts by weight) shown in Table 1,
The mixture was melt-kneaded using a twin-screw extruder (Ikegai Iron Works Co., Ltd., PCM-45), and strand-cut to prepare pellets. The obtained pellets were subjected to an injection molding machine (FN-4000, manufactured by Nissei Plastics Industry Co., Ltd.) at a cylinder temperature of 2
Injection molding was performed at 20 ° C and a mold temperature of 50 ° C.
A disc-shaped test specimen having a thickness of 2 mm and a thickness of 2 mm was prepared. The obtained test piece was kept at 25 ° C. and placed on a Tsapek agar medium inoculated with bacteria (species: E. coli) or fungi (species: Aspergillus niger), and after 48 hours, the halo was observed and the antibacterial activity was confirmed. And antifungal properties were determined. Table 2 shows the results.

Resin component: AS (acrylonitrile-styrene copolymer) Metal-based antibacterial agent component: Metal-based antibacterial agent M1 (trade name: Baicam AK, manufactured by Otsuka Chemical Co., Ltd.) Antimicrobial agent, average fiber diameter 0.2 μm, average fiber length 15 μm) Metallic antibacterial agent M2 (trade name: Zeomic, manufactured by Sinanen Zeomic Co., Ltd., a metal antibacterial agent having silver and zinc supported on zeolite) Metallic antibacterial agent M3 (brand name: Novalon AGZ330, manufactured by Toagosei Co., Ltd., a metal-based antibacterial agent in which silver and zinc are supported on zirconium phosphate) Organic antibacterial agent component: Organic antibacterial agent Y1 [TBZ (thiobendazole)] hydrophilic Resin component: polyethylene oxide-polyether-polyamide block copolymer [trade name: Perestat 6321, manufactured by Sanyo Chemical Industries, Ltd.] , ASTM D-57
Water absorption rate of 4.5% when immersed in water (23 ° C., 24 hours) about 70% by weight] Antibacterial / antifungal improver: Highly active magnesium oxide (trade name: Kyowa Mag 150 Kyowa Chemical Industry Co., Ltd.) Average particle diameter 10μm)

Evaluation ◎ A state where sufficient halo can be confirmed ○ A state where a slight halo can be confirmed △ A state where no halo appears but the test bacteria do not propagate on the test piece and the resistance is confirmed × Resistance to the test bacteria Status cannot be confirmed

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

According to the present invention, it is possible to provide a resin composition having more excellent antibacterial performance and uses of a molded article obtained therefrom.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08J 5/00 C08J 5/00 (72) Inventor Shusuke Tsutsumi 463 Kasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima In the laboratory

Claims (8)

[Claims] 1. An antibacterial or antifungal resin composition comprising a resin component (A), a metal antibacterial or antifungal component (B), and a hydrophilic component (C). 2. The resin composition according to claim 1, further comprising an organic antibacterial or antifungal component. 3. The metal-based antibacterial or antifungal component comprises potassium titanate, zenerite or zirconium phosphate carrying silver and / or zinc.
3. The resin composition according to any one of claims 1 to 2. 4. The method according to claim 1, wherein the metal-based antibacterial or antifungal component is a fibrous substance, and an inorganic substance having a shape different from that of the metal-based antibacterial or antifungal component is compounded as an antibacterial or antifungal component. Item 4. The resin composition according to any one of Items 1 to 3. 5. The method according to claim 1, wherein the hydrophilicity of the hydrophilic component is ASTM D-.
The resin composition according to claim 1, which has a water absorption of 3.5% or more according to 570. 6. A molded article obtained by molding the resin composition according to claim 1. 7. A fiber obtained by fiberizing the resin composition according to claim 1. 8. A fiber product obtained by using the fiber according to claim 7.